JP2019518111A - Method of making an article by injection molding, use of a compatibilizer in a polymer resin, and a polymer resin - Google Patents

Abstract

A method of producing an article by injection molding is disclosed, said method comprising injection molding an article from a polymer resin, said polymer resin comprising different types of recycled polymer, an inorganic particle material and said inorganic particle material And a compatibilizer comprising a surface treatment agent on the surface, wherein the polymer resin has an MFI at 2.16 kg / 190 ° C. of 3.0 g / 10 min or more. Further disclosed is the use of a compatibilizer in the article or in the polymer resin, a polymer resin suitable for use therefrom in the manufacture of the article by injection molding, and the article so produced. 【Selection chart】 None

Description

  The present invention relates to a method of producing an article by injection molding, the use of a compatibilizer in the article, the use of a compatibilizer in a polymer resin, and a polymer resin.

In recent years, recycling of polymer waste materials has begun. However, recycling of polymer waste materials presented challenges not always encountered during the preparation of polymer compositions derived from virgin polymers.
As the need to recycle polymer waste material increases, economically viable processing of polymer waste material into high quality polymer resins and articles of manufacture (portable waste containers or waste containers such as willie bins) There is a continuing need to develop new methods and compositions for.

According to a first aspect, a method of making an article by injection molding comprising injection molding an article from a polymer resin, wherein the polymer resin is a recycled polymer of a different type, and an inorganic The method is provided comprising a particulate material and a compatibilizer comprising a surface treatment agent on the surface of the inorganic particulate material, wherein the polymer resin has an MFI at 2.16 kg / 190 ° C. of 3.0 g / 10 min or more. Ru.
According to a second aspect, the use of a compatibilizer in an article, wherein said article is manufactured by injection molding a polymer resin comprising said compatibilizer, said polymer resin not comprising said compatibilizer Or exclude tiger stripes as compared to articles made by injection molding a polymer resin wherein said compatibilizer is replaced by a polymer based compatibilizer as compared to the polymer resin comprising The use for reducing the phase, wherein the compatibilizer comprises an inorganic particle material and a surface treatment agent on the surface of the inorganic particle material, and the polymer resin comprises different types of recycled polymers; The use is provided wherein the polymer resin comprising a solubilizer has an MFI at 3.16 kg / 190 ° C. of 3.0 g / 10 min or more.

According to a third aspect, the use of a compatibilizer in a polymer resin, wherein (i) the occurrence of tiger stripes is eliminated in an article produced from the polymer resin by injection molding, or (ii) the above compatibilization And / or compared to articles made by injection molding a polymer resin wherein the compatibilizer has been replaced by a polymer based compatibilizer as compared to an article made from the above polymer resin containing no agent The above use for reducing tiger stripes, wherein the compatibilizer comprises an inorganic particle material and a surface treatment agent on the surface of the inorganic particle material, and the polymer resin comprises different types of recycled polymers, The use is provided wherein the polymer resin containing the compatibilizer has an MFI at 2.16 kg / 190 ° C. of 3.0 g / 10 min or more.
According to a fourth aspect, the use of a compatibilizer in an article, wherein said article is manufactured by injection molding a polymer resin comprising said compatibilizer,
(A) (i) an article produced by injection molding the polymer resin not containing the compatibilizer, or (ii) injection molding a polymer resin in which the compatibilizer is replaced by a polymer based compatibilizer Provide a balance of superior toughness and stiffness compared to the articles produced by
(B) the above use for optimizing the balance between toughness and stiffness of the article;
The compatibilizer comprises an inorganic particle material and a surface treatment agent on the surface of the inorganic particulate material, and the polymer resin comprises different types of recycled polymers, and the polymer resin comprising the compatibilizer is 3.0 g / 10. The use is provided, having an MFI at 2.16 kg / 190 ° C. for more than a minute.

According to a fifth aspect, the use of a compatibilizer in a polymer resin wherein the article is produced by injection molding,
(A) (i) an article manufactured by injection molding the above-mentioned polymer resin not containing the above-mentioned compatibilizer, or (ii) injection of a polymer resin in which the above-mentioned compatibilizer is replaced by the compatibilizer based on polymer Provide a balance of superior toughness and stiffness compared to articles produced by molding, or
(B) the above use for optimizing the balance between toughness and stiffness of the article;
The compatibilizer comprises an inorganic particulate material and a surface treatment agent on the surface of the inorganic particulate material, the polymeric resin comprises a different type of recycled polymer, and the polymeric resin comprises 3.0 g of the compatibilizer The use is provided, having an MFI at 2.16 kg / 190 ° C. for 10 minutes or more.
According to a sixth aspect, a polymer resin suitable for use in the manufacture of articles therefrom by injection molding, wherein said polymer resin is different and based on the total weight of said recycled polymer and said polymer resin The polymer resin comprises about 5% by weight to about 20% by weight of a mixture of an inorganic particle material and a compatibilizer containing a surface treatment agent on the surface of the inorganic particle material, wherein the polymer resin is at least 3.0 g / 10 min. About 10% by weight based on the total weight of the polymer resin and about 50% by weight recycled polyethylene having a MFI at 190 ° C. or higher and the polymer resin based on the total weight of the polymer composition The above polymer resin is provided, comprising-about 30% by weight recycled polypropylene.

Figure 1 is a photograph of an article made by injection molding a polymer resin containing a polymer based compatibilizer. Figure 2 is a photograph of an article made by injection molding a polymer resin according to the present invention.

  Manufacturing plastics from mixed polymer feedstocks, such as recycled polymers, can be challenging due to incompatibilities between different polymer times, such as immiscibility between polyethylene and polypropylene. Efforts to improve compatibility will be hampered due to the tension between the different mechanical properties of plastics made from such mixed polymer feeds. More particularly, it can be difficult to balance the properties of mechanical properties such as strength and stiffness of the final product, such as those formed by injection molding. Surprisingly, the inventors balance or optimize mechanical properties such as strength and stiffness by the use of a compatibilizer comprising an inorganic particle material and a surface treatment agent on the surface of said inorganic particle material. I found that it was achievable.

Polymeric Resin The polymeric resin of the present invention comprises different types of recycled polymer and a compatibilizer comprising an inorganic particle material and a surface treatment agent on the surface of the inorganic particle material.
In one embodiment, the polymer resin comprises polyethylene and polypropylene, or a mixture of different types of polyethylene (eg, HDPE, LDPE and / or LLDPE) and polypropylene, or a mixture of different types of HDPE and polypropylene.
In certain embodiments, the polymer resin comprises about 90 wt% or less, such as about 80 wt% or less, or about 70 wt% or less, or about 60 wt% or less, or about 50 wt% or less of polypropylene. It is included in an amount of not more than mass%, or not more than about 35 mass%, or not more than about 30 mass%.
Unless otherwise stated, the amount of polymer resin component described herein is based on the total weight of the polymer resin.
In one embodiment, the polymer resin comprises 20-40 wt% polypropylene, such as 20-35 wt% polypropylene, or 23-30 wt% polypropylene, or 23-28 wt% polypropylene.
In one embodiment, all of the polypropylene in the polymer resin is recycled polypropylene.

In some embodiments, all or at least a portion of the polypropylene, such as at least 50%, or at least 75%, or at least about 90%, or at least 90%, or at least 95%, or at least 99%, or at least 99.9% , A recycled mixed polyolefin stream containing polypropylene.
In certain embodiments, the polymer resin comprises at least about 10%, such as at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 10% by weight of polyethylene. Included in an amount of 60% by weight. In one embodiment, the polymer resin comprises a major amount of polyethylene, the major amount being defined as greater than 50% by weight. In certain embodiments, the polymer resin comprises about 90 wt% or less, such as about 80 wt% or less, or about 75 wt% or less, or about 60 wt% or less, or about 50 wt% or less of polyethylene. Included in an amount of less than or equal to about 30% by weight In one embodiment, the polymer resin comprises polyethylene in an amount of about 50-80% by weight, for example about 60-75% by weight.
The polyethylene is at least two different types of polyethylene, such as at least two different types of recycled polyethylene, such as recycled HDPE and at least one other type of polyethylene from another recycled source, For example, HDPE can be included.

In one embodiment, the polymer resin comprises a mixture of different types of polyethylene, such as HDPE, LDPE and / or LLDPE. In general, HDPE is understood to be primarily linear or unbranched polyethylene polymers with relatively high crystallinity and melting point, and densities of about 0.96 g / cm ³ or more. Generally, LDPE (low density polyethylene) it is understood to be a relatively low crystallinity and melting point, and about 0.91 g / cm ³ ~ about high branched polyethylene having a density of 0.94 g / cm ^3. In general, LLDPE (linear low density polyethylene) is understood to be a polyethylene with a significant number of short branches commonly produced by the copolymerization of ethylene and long chain olefins. LLDPE is structurally different from conventional LDPE because of the absence of long chain branching.
In one embodiment, the polymer resin comprises two different types of HDPE, and each type of HDPE is present in an amount of 20-40% by weight based on the total weight of the polymer resin. In one embodiment, the first type of HDPE is present in an amount of 20 to 30% by weight and the second type of HDPE is present in an amount of 30 to 40% by weight. In one embodiment, both types of HDPE are derived from recycled polymer sources, such as post-consumer polymer waste.
In one embodiment, at least 75% by weight, for example 90 to 99% by weight of the polymer in the polymer resin is a mixture of polyethylene and polypropylene, for example, a mixture of HDPE and polypropylene (in the resin composition) Based on the total mass of the polymer). In one embodiment, all of the polymers in the polymer resin are polyethylene or polypropylene.

In certain embodiments, the HDPE, when present, is a mixture of post-consumer polymer wastes of different types, eg, recycled blow molded HDPE and / or HDPE from recycled injection molded HDPE, from different sources .
In some embodiments, all or at least a portion (eg, at least 50%, or at least 75%, or at least about 90%, or at least 90%, or at least 95%, or at least 99%) of the polymer component of the polymer resin. Or at least 99.9%) originates from polymer waste, such as post consumer polymer waste, post industrial polymer waste and / or post agricultural waste polymer. In some embodiments, all or at least a portion (eg, at least 50%, or at least 75%, or at least about 90%, or at least 90%, or at least 95%, or at least 99%) of the polymer component of the polymer resin. Or at least 99.9%) is or originate from recycled post-consumer polymer waste.
In some embodiments, the polyethylene, such as HDPE, is about 5.0 g / min or less, such as about 1.0 g / min to 5.0 g / min, or about 2.0 g / min to about 5.0 g / min, or about 3.0 g / min. It has an MFI at 2.16 kg / 190 ° C. for minutes to about 5.0 g / min. In an embodiment where the polymer resin comprises two or more types of polyethylene, such as two or more types of HDPE, the MFI of the two or more polyethylenes at 2.16 kg / 190 ° C. is about 3.0 g / min. The following may differ, for example up to about 2.0 g / min, or up to about 1.5 g / min.

In certain embodiments, the polypropylene has a content of about 5.0 g / min or more, such as about 5.0 g / 10 min to about 10 g / min, or about 5.0 g / about 9.0 g / min, or about 5.0 g / min to about 8.0 g MFI / minute, or about 5.0 g / min to about 7.5 g / min, or about 5.5 g / min to about 7.0 g / min, or about 6.0 g / min to about 7.0 g / min 2.16 kg / 190 ° C. Have.
In certain embodiments, the polymer resin is about 20 wt% or less of a virgin polymer, such as about 10 wt% or less of a virgin polymer, or about 5 wt% or less of a virgin polymer, based on the total weight of the resin composition. The polymer, or about 1 wt% or less of virgin polymer, or about 0.1 wt% or less of virgin polymer.
In one embodiment, the polymer resin is substantially free of virgin polymer, for example, the polymer resin is free of virgin polymer.
In one embodiment, all of the polymers in the resin composition are recycled polymers derived from polymer waste, such as, for example, post-consumer waste.
In some embodiments, the polymer resin (i.e., including the optional ingredients added and the compatibilizing agent) is greater than about 0.925 g / cm ^3, for example, from about 0.95 g / cm ³ or more, about 0.975 g / cm ^It has a density of ³ or more, or about 1.00 g / cm ³ or more. In some embodiments, the density is about 1.25 g / cm ³ or less, such as about 1.10 g / cm ³ or less, or about 1.05 g / cm ³ or less. Density can be measured according to ISO 1183.

For use in certain applications, such as wheelie bin applications, the above-mentioned polymer resins have to fulfill certain requirements, for example in terms of MFI (melt flow index). One such requirement is that the MFI of the above polymer resin at 2.16 kg / 190 ° C. must be at least 3.0 g / 10 min.
MFI as referred to herein is measured according to ISO 1133.
The polymer resin of the present invention has an MFI at 2.16 kg / 190 ° C. of 3.0 g / 10 min or more. In certain embodiments, the polymer resin is about 3.1 g / 10 minutes or more, such as about 3.2 g / 10 minutes or more, or about 3.3 g / 10 minutes or more, or about 3.4 g / 10 minutes or more, or about 3.5 g It has an MFI at 2.16 kg / 190 ° C. over 10 minutes.
In certain embodiments, the polymer resin is about 5 g / 10 min or more, such as about 6 g / 10 min or more, or about 6.5 g / 10 min or more, or about 6.7 g / 10 min or more, or about 6.9 g / 10 min. Has an MFI at 5.0 kg / 230 ° C. for more than a minute.

In one embodiment, the polymer resin comprises 40 to 95 wt% polypropylene, for example 60 to 95 wt% polypropylene, or 65 to 95 wt% polypropylene. In one embodiment, the polymer resin comprises 40-70% by weight polypropylene, such as 60-70% by weight polypropylene, or 65-70% by weight polypropylene. In such embodiments, the polymeric resin can include a peroxide containing additive, such as a peroxide containing additive, in the amounts described herein. In such embodiments, the polymeric resin can comprise up to about 30% by weight polyethylene, such as about 20-30% by weight polyethylene, or about 20-25% by weight polyethylene. The polyethylene may be HDPE. In such an embodiment, all of the above polypropylene and polyethylene can be recycled polypropylene and polyethylene. In such embodiments, the polypropylene is 5.0 g / 10 min or more, such as about 5.0 g / 10 min to about 10 g / min, or about 5.0 g / 10 min to about 8.0 g / min, or about 6.0 g It can have an MFI at 2.16 kg / 190 ° C./min to about 7.0 g / min. In such embodiments, the polyethylene, eg, HDPE, is about 2.0 g / min or less, such as about 1.0 g / min or less, or about 0.1 g / min to about 0.8 g / min, or about 0.2 g / min to It can have an MFI at about 0.7 g / min, or about 0.4 g / min to about 0.6 g / min 2.16 kg / 190 ° C.
In one embodiment, the resin composition further comprises an antioxidant, for example in an amount of less than about 5% by weight, such as less than about 1% by weight. In certain embodiments, the resin composition further comprises an antioxidant, for example, in an amount of about 0.1 to 1% by weight, or about 0.1 to 0.5% by weight, or about 0.3% by weight.

In one embodiment, the polymer resin is about 5 wt% to about 20 wt% of the inorganic particle material and the surface of the inorganic particle material based on the mixture of different recycled polymers and the total weight of the polymer resin. The polymer resin has a MFI of 2.16 kg / 190 ° C. of 3.0 g / 10 min or more, and the polymer resin is based on the total weight of the polymer composition About 10% by weight to about 30% by weight, based on the total weight of the polymer composition, based on at least about 50% by weight recycled polyethylene (which may be a mixture of at least two different types of HDPE) It may comprise wt% recycled polyethylene and may further comprise up to about 10 wt% impact modifier and up to about 1.0 wt% antioxidant. In this embodiment, the polymer resin is suitable for use in the manufacture of an article therefrom by injection molding. In one embodiment, the polymer resin comprises about 50-70% by weight of polyethylene (which may be a mixture of at least two different types of HDPE), 20-30% by weight of polypropylene, and 5-15. It may comprise wt% of a compatibilizer and may further comprise about 1 to 7.5 wt% of an impact modifier and up to about 0.5 wt% of an antioxidant.
The above polymer resins as defined herein can be prepared by any known suitable manufacturing method. In one embodiment, the polymer resin is prepared by melt mixing an appropriate blend of the components in an extruder such as a Coperion ZSK ¹⁸ twin screw extruder (diameter 18 mm). The screw speed can be set to 800 rpm and the feed rate to 8.0 kg / hour. In such embodiments, the hot extrudate may then be immediately quenched in water and pelletized.

Compatibilizer The above-mentioned polymer resin of the present invention contains a compatibilizer comprising an inorganic particle material and a surface treatment agent on the surface of the inorganic particle material.
The compatibilizer may be present in the resin composition in an amount ranging from about 1 wt% to about 45 wt% based on the total weight of the resin composition. For example, about 2 wt% to about 40 wt%, or about 3 wt% to about 35 wt%, or about 4 wt% to about 30 wt%, or about 5 wt%, based on the total weight of the resin composition. To about 30 wt%, or about 5 wt% to about 25 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, Or about 7% by weight to about 13% by weight, or about 8% by weight to about 12% by weight.
The surface treatment agent (i.e., the coupling regulator) is about 0.01 wt% to about 4 wt% based on the total weight of the resin composition, for example, about 0.02 wt% based on the total weight of the resin composition. Wt% to about 3.5 wt%, or about 0.05 wt% to about 1.4 wt%, or about 0.1 wt% to about 0.7 wt%, or about 0.15 wt% to about 0.7 wt%, about 0.3 wt% to about 0.7 wt% Or about 0.5 wt% to about 0.7 wt%, or about 0.02 wt% to about 0.5 wt%, or about 0.05 wt% to about 0.5 wt%, or about 0.1 wt% to about 0.5 wt%, or about 0.15 wt% It may be present in the resin composition in an amount of from about 0.5% by weight, or from about 0.2% by weight to about 0.5% by weight, or from about 0.3% by weight to about 0.5% by weight.

  In one embodiment, the surface treatment agent comprises a first compound comprising a terminal propanoic acid group or ethylene group having one or two adjacent carbonyl groups. The surface treatment agent may be coated on the surface of the inorganic particles. The purpose of the surface treatment agent (e.g. coating) is to improve the compatibility of the inorganic particle material with the polymer matrix to be combined and / or by crosslinking or grafting different polymers into the polymer resin 2 It is to improve the compatibility of more than one different polymer. In recycled polymer resin compositions that include recycled polymer and may include virgin polymer, the inorganic particulate material coating can serve to crosslink or graft the different polymers. While not wishing to be bound by theory, the coupling may be physical (eg, steric) and / or chemical (eg, chemical bonding, eg, covalent bonding) between the polymer and the surface treatment agent. Or van der Waals) thought to involve interactions.

In one embodiment, the surface treatment agent (ie, the coupling modifier) has the formula (1):
A- (XY-CO) _m (OB-CO) _n OH (1)
(In the formula,
A is a moiety containing a terminal ethylene bond having one or two adjacent carbonyl groups;
X is O, m is 1 to 4 or X is N and m is 1;
Y is C _1-8 -alkylene or C _2-18 -alkenylene;
B is C _2-6 -alkylene; n is 0 to 5;
However, when A contains two carbonyl groups adjacent to an ethylene group, X is N).

In one embodiment, AX- is a residue of acrylic acid, (OB-CO) _n may be δ-lactone or ε-caprolactone or a mixture thereof and n may be 0.
In another embodiment, AX- is a residue of maleimide and (0-B-CO) _n may be a residue of δ-valerolactone or ε-caprolactone or a mixture thereof, n is 0 It may be.
Specific examples of coupling regulators are β-carboxyethyl acrylate, β-carboxyhexyl maleimide, 10-carboxydecyl maleimide and 5-carboxypentyl maleimide.
Exemplary coupling modifiers and methods for their preparation are described in US Pat. No. 7,732,514, the entire contents of which are incorporated herein.

In another embodiment, the coupling regulator is β-acryloyloxypropanoic acid or oligomeric acrylic acid of formula (2):
CH ₂ = CH-COO [CH ₂ -CH ₂ -COO] _n H (2)
(Wherein n represents a number of 1 to 6).

In one embodiment, n is 1 or 2 or 3 or 4 or 5 or 6.
The above-mentioned oligomeric acrylic acid of the formula (2) is in the range of about 50 ° C. to 200 ° C., with acrylic acid in the presence of 0.001 to 1% by weight of a polymerization inhibitor, optionally under high pressure and in the presence of an inert solvent. It can be prepared by heating to a temperature of Exemplary coupling modifiers and methods for their preparation are described in US Pat. No. 4,267,365, the entire contents of which are incorporated herein.
In another embodiment, the coupling regulator is β-acryloyloxypropanoic acid. This species and its method of manufacture are described in US-A-3888912, the entire content of which is incorporated herein.

  The surface treatment / coupling modifier is present in the compatibilizer in an amount effective to achieve the desired result. This varies among the coupling modifiers and may depend on the exact composition of the inorganic particles. For example, the coupling modifier may be present in an amount of about 5 wt% or less, such as about 2 wt% or less, or such as about 1.5 wt% or less, based on the total weight of the compatibilizer. In one embodiment, the coupling modifier, in the compatibilizer, is about 1.2 wt% or less, such as about 1.1 wt% or less, such as about 1.0 wt% or less, based on the total weight of the compatibilizer Up to about 0.9% by weight, such as up to about 0.8% by weight, such as up to about 0.7% by weight, such as up to about 0.6% by weight, such as up to about 0.5% by weight, such as up to about 0.4% by weight, such as up to about 0.3% by weight, such as It is present in an amount of not more than 0.2% by weight, or such as not more than about 0.1% by weight. Typically, the coupling modifier is present in the compatibilizer in an amount greater than about 0.05% by weight. In a further embodiment, the coupling modifier is about 0.1 to 2 wt%, such as about 0.2 wt% to about 1.8 wt%, or about 0.3 to about 1.6 wt%, or about 0.4 to about 2 wt% in the compatibilizer. About 1.4 wt%, or about 0.5 to about 1.3 wt%, or about 0.6 to about 1.2 wt%, or about 0.7 to about 1.2 wt%, or about 0.8 to about 1.2 wt%, or about 0.8 to about 1.1 wt% Exist in range quantities.

In one embodiment, the compound / compounds containing terminal propanoic acid groups or ethylene groups having one or two adjacent carbonyl groups is the only chemical present in the surface treatment agent. It is a species.
In one embodiment, the surface treatment agent further comprises a second compound selected from the group consisting of one or more fatty acids and salts of one or more fatty acids, and combinations thereof.
In one embodiment, the one or more fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapietic acid, oleic acid And elidic acid, vaccenic acid, linoleic acid, linolenic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid and combinations thereof. In another embodiment, the one or more fatty acids are saturated fatty acids or unsaturated fatty acids. In another embodiment, the fatty acid, C ₁₂ -C ₂₄ fatty acids, for example, a C ₁₆ -C ₂₂ fatty acids which may be saturated or unsaturated. In one embodiment, the one or more fatty acids are stearic acid and may be combined with other fatty acids.
In another embodiment, the one or more salts of fatty acids are metal salts of fatty acids as described above. The metal may be an alkali metal or alkaline earth metal or zinc. In one embodiment, the second compound is calcium stearate.

  The second compound, if present, is present in the compatibilizer in an amount effective to achieve the desired result. This varies between coupling modifiers and may depend on the exact composition of the inorganic particles. For example, the second compound may be present in an amount of about 5 wt% or less, such as about 2 wt% or less, such as about 1 wt% or less based on the total weight of the compatibilizer. In one embodiment, the second compound is about 0.9 wt% or less, such as about 0.8 wt% or less, such as about 0.7 wt% or less, such as about 0.6 wt% or less, based on the total weight of the compatibilizer. For example, it may be present in an amount of about 0.5 wt% or less, such as about 0.4 wt% or less, such as about 0.3 wt% or less, such as about 0.2 wt% or less, such as about 0.1 wt% or less. Typically, the second compound, if present, may be present in the compatibilizer in an amount greater than about 0.05% by weight. The mass ratio of the coupling regulator to the second compound is about 5: 1 to about 1: 5, for example about 4: 1 to about 1: 4, for example about 3: 1 to about 1: 3, for example 2: 1 to 1: 2 or, for example, about 1: 1. The amount of coating comprising the first compound (i.e., the coupling regulator) and the second compound (i.e., the one or more fatty acids or salts thereof) provides a monolayer coating on the surface of the inorganic particles. May be calculated as: In embodiments, the weight ratio of the first compound to the second compound is about 4: 1 to about 1: 3, for example about 4: 1 to about 1: 2, for example about 4: 1 to about 1 For example about 4: 1 to about 2: 1, such as about 3.5: 1 to about 1: 1, such as about 3.5: 1 to 2: 1 or such as about 3.5: 1 to about 2.5: 1.

In one embodiment, the surface treatment agent does not include a compound selected from the group consisting of one or more fatty acids and one or more salts of fatty acids.
In one embodiment, the surface agent is or comprises an organic linker on the surface of the inorganic particle. The organic linker has oxygen containing acid functionality. The organic linker is a base form of an organic acid. By "base form" is meant that the organic acid is at least partially deprotonated, for example by dehydrating the organic acid to form the corresponding oxyanion. In one embodiment, the base form of the organic acid is a conjugated base of the above organic acid. The organic acid (and thus the organic linker) comprises at least one carbon-carbon double bond.
In one embodiment, the organic linker is a non-polymeric species, and in one embodiment, has a molecular weight of about 400 g / mol or less. "Non-polymer" refers to (i) chemical species not formed by polymerization of monomeric species, and / or (ii) relatively low molecular weight, for example a molecular weight less than about 1000 g / mol, for example a molecular weight less than about 400 g / mol By chemical species is meant and / or (iii) chemical species containing up to 70 carbon atoms in the carbon chain, eg up to about 25 carbon atoms in the carbon chain.

In certain embodiments, the non-polymeric species is about 800 g / mol or less, or about 600 g / mol or less, or about 500 g / mol or less, or about 400 g / mol or less, or about 300 g / mol or less, or about 200 g It has a molecular weight of at most / mol. Alternatively or additionally, in some embodiments, the non-polymeric species has about 50 or less carbon atoms, or about 40 or less carbon atoms, or about 30 or less carbon atoms, or about 25 Or less, or about 20 or less carbon atoms, or about 15 or less carbon atoms.
In one embodiment, the compatibilizer comprises a particle and an organic linker on the surface of the particle (which acts as a coupling regulator), and the compatibilizer comprises at least an organic acid having oxygen-containing acid functionality. It is obtained by partial dehydration and contains at least one carbon-carbon double bond in the presence of the particles.

(式中、Rは、各々、少なくとも1つの炭素-炭素二重結合を含む不飽和C₂₊基である)。
上記カルボキシレート基(これはオキシアニオン)が共鳴形態で示される。上記カルボキシレート基は共役塩基の一例である。ある実施態様においては、Rは、不飽和C₃₊基、または不飽和C₄₊基、または不飽和C₅₊基である。 Exemplary organic acids are carboxylic acids and their base forms carboxylates, eg,

Wherein R is an unsaturated C ₂₊ group each containing at least one carbon-carbon double bond.
The carboxylate group (which is an oxyanion) is shown in resonant form. The carboxylate group is an example of a conjugated base. In one embodiment, R is an unsaturated C ₃₊ group, or an unsaturated C ₄₊ group, or an unsaturated C ₅₊ group.

  While not wishing to be bound by theory, it is believed that the acid functional base form coordinates / associates with the surface of the particle, and the organic tail having at least one carbon-carbon double bond is in the resin composition. It is believed to coordinate / associate with different polymer species. Thus, the compatibilizer acts to crosslink or graft different polymer types by means of an organic linker acting as a coupling regulator, the coupling being physical (eg steric) between different polymers and between polymers and particles. And / or chemical (eg, covalent bonds or chemical bonds such as van der Waals, eg, chemical bond interactions). The overall effect is to enhance the compatibility of the different polymer types in the polymer resin, which is also due to the treatment of the polymer resin and / or a portable waste container or waste object produced from the polymer resin. It will enhance one or more physical properties (eg, one or more mechanical properties) of the container, eg, an article of manufacture such as willie bin. The surface of the particle can serve to balance the anionic charge of the organic linker. Furthermore, the compatibilizing effect may allow to incorporate higher amounts of particles without adversely affecting the processability of the polymer blend and / or the physical properties of the articles produced from the polymer blend. This can also reduce costs due to the low use of polymers (such as those that are recycled).

In one embodiment, the organic linker is an organic acid, such as a carboxylate or phosphate or a phosphite or phosphinate or a conjugated base of an amino acid. In one embodiment, the organic linker is a carboxylate. In another embodiment, the organic linker includes a maleimide ring (e.g., an amide carboxylate functionality coordinates / associates with the surface of the particle, and a carbon-carbon double bond is in the polymer resin). Coordinate / associate with different polymer species).
In one embodiment, the organic linker comprises at least one carbon atom in addition to the carbon-carbon double bond. In certain embodiments, the organic linker comprises, in addition to a carbon-carbon double bond, at least 2 carbon atoms, or at least 3 carbon atoms, or at least 4 carbon atoms, or at least 5 carbons. Contains atoms In one embodiment, the organic linker comprises a chain of at least 6 carbon atoms, for example, a chain of at least 6 carbon atoms including at least one carbon-carbon double bond. In one embodiment, the organic linker comprises only one carbon-carbon double bond. In one embodiment, the organic linker comprises two carbon-carbon double bonds. In one embodiment, the organic linker comprises three carbon-carbon double bonds. The moiety with respect to the at least one carbon-carbon double bond can be arranged in a cis or trans configuration. The carbon-carbon double bond may be a terminal group or may be internal to the molecule, ie within a chain of carbon atoms.

In one embodiment, the organic linker has the formula:
(1) CH ₂ = CH- (CH ₂ ) _a -Z
And / or
(2) CH _3- (CH ₂ ) _b -CH = CH- (CH ₂ ) _c -Z
(In the formula,
a is 3 or more;
b is 1 or more, c is 0 or more, but b + c is at least 2;
Z is a carboxylate group, a phosphate group, a phosphite group or a phosphinate group).

In certain embodiments, a is 6-20, such as 6-18, or 6-16, or 6-14, or 6-12, or 6-10, or 7-9. In one embodiment, a is 8.
In some embodiments, b and c are each independently 4 to 10, eg, each independently 5 to 11, or 5 to 10, or 6 to 9, or 6 to 8. In one embodiment, b and c are both 7.
In one embodiment, when the organic linker has the formula (1), Z is a carboxylate group. In such embodiments, the compatibilizer may consist essentially of or consist of particles (eg, inorganic particles) and the organic linker of Formula (1), wherein Z is carboxy It is a rate group.
In one embodiment, when the organic linker has the formula (2), Z is a carboxylate group. In such embodiments, the compatibilizer may consist essentially of or consist of particles (eg, inorganic particles) and the organic linker of Formula (2), wherein Z is a carboxylate It is a group.
In one embodiment, the organic linker is a mixture of formula (1) and formula (2), and Z may be in each case a carboxylate group. In such embodiments, the compatibilizer comprises particles (eg, inorganic particles), the organic linker of Formula (1) (Z is a carboxylate group), and the organic linker of Formula (2) ( Z may consist essentially of or consist of a carboxylate group).

In one embodiment, the organic acid is an unsaturated fatty acid or derived from an unsaturated fatty acid. In one embodiment, where the organic acid is an unsaturated fatty acid, the compatibilizer consists essentially of or consists of particles (eg, inorganic microparticles) and an organic linker. In such embodiments, the unsaturated fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, It may be selected from one of erucic acid and docosahexaenoic acid. In such embodiments, the unsaturated fatty acid may be oleic acid, ie, in one embodiment, the compatibilizer comprises particles (eg, inorganic particles) and a base form of oleic acid. In one embodiment, the compatibilizer comprises particles (eg, inorganic particles) and a base form of oleic acid.
In one embodiment, the organic acid is derived from unsaturated fatty acids. In one embodiment, the organic acid is undecylenic acid, ie, the organic linker is the base form of undecylenic acid. In one embodiment, the compatibilizer comprises particles (eg, inorganic particles) and the base form of undecylenic acid.

Inorganic Particulate Material The inorganic particulate material may be, for example, an alkaline earth metal carbonate or sulfate, such as calcium carbonate, magnesium carbonate, dolomite, gypsum, kaolin, hydrous kandite clay such as halloysite or ball clay, metakaolin or completely It may be anhydrous (calcined) kandite clay such as calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminum trihydrate, or a combination thereof.
The preferred inorganic particulate material is calcium carbonate. Hereinafter, the present invention may tend to be described with respect to calcium carbonate and with respect to the manner in which the calcium carbonate is manufactured and / or treated. The present invention should not be construed as limited to such embodiments.
The particulate calcium carbonate used in the present invention can be obtained from natural sources by grinding. Ground calcium carbonate (GCC) is typically ground into a mineral source such as chalk, marble or limestone to obtain a product with the desired degree of fineness, followed by a particle size classification step It is obtained by doing. Other techniques such as bleaching, flotation and magnetic separation can also be used to obtain products with the desired degree of fineness and / or color. The particulate solid material can be ground spontaneously, ie by abrasion between the particles of the solid material itself, or in the presence of a particulate grinding medium comprising particles of a material different to the calcium carbonate to be ground. It can be crushed. These processes can be carried out in the presence or absence of dispersants and biocides, which can be added at any stage of the process.

  Precipitated calcium carbonate (PCC) can be used as a source of particulate calcium carbonate in the present invention and can be produced by any of the known methods available in the art. TAPPI Monograph Series No 30, "Paper Coating Pigments", pages 34-35, are three major commercial methods for preparing precipitated calcium carbonate suitable for use in the preparation of products for use in the paper industry However, it may be used in the practice of the present invention. In all three processes, a calcium carbonate feedstock such as limestone is first calcined to form quicklime, and then the quicklime is digested in water to obtain calcium hydroxide or lime milk. In the first process, lime milk is directly carbonated with carbon dioxide. This process has the advantage that no by-products are formed and the properties and purity of the calcium carbonate product are relatively easy to control. In the second process, lime milk is contacted with soda ash to produce a precipitate of calcium carbonate and a solution of sodium hydroxide by metathesis. Sodium hydroxide can be substantially completely separated from calcium carbonate when this process is used commercially. In the third major commercial process, lime milk is first contacted with ammonium chloride to obtain calcium chloride solution and ammonia gas. The calcium chloride solution is then contacted with soda ash to produce precipitated calcium carbonate and sodium chloride solution by metathesis. Crystals can be produced in a variety of different shapes and sizes, depending on the particular reaction process used. The three major forms of PCC crystals are aragonite, rhombohedra and spheroid, all of which mixtures are suitable for use in the present invention.

Wet grinding of calcium carbonate involves the formation of an aqueous suspension of calcium carbonate that may be ground, and may be in the presence of a suitable dispersant. For further information on wet grinding of calcium carbonate, reference can be made, for example, to EP-A-614948, the content of which is incorporated in its entirety. The inorganic particles, such as calcium carbonate, can also be prepared by any suitable dry grinding technique.
In some circumstances, for example, the addition of kaolin, calcined kaolin, wollastonite, bauxite, talc, titanium dioxide or other minerals where one or more of mica may be present may be included.
If the inorganic particulate material is obtained from a natural source, some inorganic impurities may contaminate the ground material. For example, naturally occurring calcium carbonate can be present in association with other minerals. Thus, in some embodiments, the inorganic particulate material contains an amount of impurities. However, in general, the above inorganic particulate material used in the present invention contains less than about 5% by weight, preferably less than about 1% by weight of other mineral impurities.

Unless otherwise stated, the particle size properties referred to herein for the above inorganic particle materials are used in the field of laser light scattering, using a CILAS 1064 instrument (or other method which produces essentially the same results) It is measured by a known conventional method. In the above laser light scattering technique, the size of particles in powders, suspensions and emulsions can be measured using diffraction of the laser beam based on the application of Mie theory. Such machines provide a measure and plot of the cumulative percentage by volume of particles whose size is smaller than a predetermined esd value, referred to in the art as "equivalent spherical diameter" (esd). The average particle size d ₅₀ is the value thus determined of particles esd of which 50% by volume of particles have an equivalent spherical diameter smaller than this d ₅₀ value. The term d ₉₀ is the particle is a particle size value less than 90% by volume.
The d ₅₀ of the inorganic fine particles is less than about 100 μm, such as less than about 80 μm, such as less than about 60 μm, such as less than about 40 μm, such as less than about 20 μm, such as less than about 15 μm, such as less than about 10 μm, such as less than about 8 μm, such as about 6 μm For example, less than about 5 μm, such as less than about 4 μm, such as less than about 3 μm, such as less than about 2 μm, such as less than about 1.5 μm, such as less than about 1 μm. The d ₅₀ of the inorganic particles may be about 2.5 μm or less, such as about 1.0 μm or less or about 0.75 μm. The d ₅₀ of the inorganic fine particles may be more than about 0.5 μm, such as more than about 0.75 μm, such as more than about 1.25 μm, such as more than about 1.5 μm. The d ₅₀ of the inorganic fine particles is 0.5 to 20 μm, for example about 0.5 to 10 μm, for example about 1 to about 5 μm, for example about 1 to about 3 μm, for example about 1 to about 2 μm, for example about 0.5 to about 2 μm, for example about 0.5 About 1.5 μm, such as about 0.5 to about 1.4 μm, such as about 0.5 to about 1.4 μm, such as about 0.5 to about 1.3 μm, such as about 0.5 to about 1.2 μm, such as about 0.5 to about 1.1 μm, such as about 0.5 to about 1.0 It may be in the range of μm, such as about 0.6 to about 1.0 μm, such as about 0.7 to about 1.0 μm, such as about 0.6 to about 0.9 μm, such as about 0.7 to about 0.9 μm.

The d ₉₀ (also referred to as top cut) of the inorganic fine particles is less than about 150 μm, such as less than about 125 μm, such as less than about 100 μm, such as less than about 75 μm, such as less than about 50 μm, such as less than about 25 μm, such as less than about 20 μm It may be less than 15 μm, such as less than about 10 μm, such as less than about 8 μm, such as less than about 6 μm, such as less than about 4 μm, such as less than about 3 μm, or such as less than about 2 μm. Advantageously, the d ₉₀ may be less than about 25 μm.
The amount of particles smaller than 0.1 μm is typically less than or equal to about 5% by volume.

The inorganic particles can have a particle steepness of about 10 or more. The particle gradient (ie, the gradient of the particle size distribution of the above inorganic particles) is determined by the following equation:
Gradient _{= 100 × (d 30 / d} 70),
(Wherein, _{d. 3O} is the value of the particle esd particles is 30 vol% having an esd less than the _{d. 3O} value, d ₇₀ is the 70 vol% particle having an esd less than the d ₇₀ value Is the value of some particles esd).

The inorganic particulates may have a particle gradient of about 100 or less. The inorganic particulates may have a particle gradient of about 75 or less, about 50 or less, or about 40 or less, or 30 or less. The inorganic particles may have a particle gradient of about 10 to about 50, or about 10 to about 40.
The inorganic particles are treated with a surface treatment agent, ie, a coupling regulator, so as to apply a surface treatment to the surface. In one embodiment, the inorganic fine particles are coated with a surface treatment agent.
In one embodiment, the inorganic particulate material of the compatibilizer is calcium carbonate, such as GCC.
According to certain aspects and embodiments thereof, the resin composition substantially comprises a peroxide containing additive such as dicumyl peroxide or 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane. Not included, ie not included.

  Alternatively, in certain embodiments and embodiments thereof, the resin composition comprises a peroxide-containing additive such as dicumyl peroxide or 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane. . The peroxide-containing additive does not necessarily have to be included in the surface treatment agent / coupling regulator, but instead is added in the formulation of the compatibilizer and the polymer, as described below. It is also good. In polymer systems containing some polymer systems, such as polyethylene (e.g. HDPE), the inclusion of peroxide-containing additives can promote crosslinking of the polymer chains. For other polymer systems, such as polypropylene, the inclusion of peroxide-containing additives can facilitate the cleavage of polymer chains. The peroxide-containing additive may be present in an amount effective to achieve the desired result. This will vary between coupling modifiers and may depend on the precise composition of the inorganic particulate and the polymer. For example, the peroxide-containing additive is less than or equal to about 1 wt%, such as about 0.5 wt%, such as about 0.5 wt%, based on the weight of the polymer in the resin composition to which the peroxide-containing additive is to be added. 0.1 mass%, for example about 0.09 mass% or less, or for example about 0.08 mass% or less, or for example about 0.06 mass% or less, about 0.05 mass% or less, about 0.04 mass% or less, about 0.03 mass% or less, about 0.02 mass% or less And may be present in amounts of up to about 0.01% by weight. Typically, the peroxide-containing additive, if present, is greater than about 0.001 wt%, such as about 0.005 wt% or more, such as about about 75 wt%, based on the weight of the polymer in the resin composition. It is present in an amount of at least 0.075% by weight, or at least about 0.01% by weight.

The compatibilizer comprises an inorganic particle, a surface treatment agent / coupling regulator and optionally a peroxide-containing additive, preferably at a temperature of 80 ° C. or less, for example using a Steele and Cowlishaw high-intensity mixer It can be prepared by mixing in The compound of the surface treatment agent / coupling regulator may be applied before the addition of the inorganic particles to the optionally recycled polymer composition, even after grinding the inorganic particles. For example, in the step of mechanically deagglomerating the inorganic particles, the surface treatment agent / coupling regulator may be added to the inorganic particles. The surface treatment / coupling modifier may be applied during the deagglomeration carried out in the mill.
The compatibilizer can further include an antioxidant. Suitable antioxidants include, but are not limited to, organic molecules consisting of hindered phenols and amine derivatives, organic molecules consisting of phosphoric acid esters and low molecular weight hindered phenols, and thioesters. Exemplary antioxidants include Irganox 1010 and Irganox 215, and blends of Irganox 1010 and Irganox 215. Alternatively, such an antioxidant may be added to the resin composition separately from the above-mentioned compatibilizer. Alternatively, a portion of the total required amount of antioxidant may be present in both of the above compatibilizers, and may be added to the resin composition separately from the above compatibilizers.

Second Filler In one embodiment, the resin composition, when present, includes a filler, ie, one or more second filler components, in addition to the compatibilizer. The second filler component can not be treated with a surface treatment / coupling modifier. In one embodiment, the second filler component is not treated with a surface treatment / coupling modifier. Such additional components, when present, are suitably selected from known filler components for polymer compositions. For example, the above-described inorganic particles used in functional fillers can be used with one or more other known second filler components such as, for example, carbon black and / or talc.
In one embodiment, the resin composition comprises carbon black as a second filler component. The carbon black can function as a colorant and / or a UV stabilizer.
In some embodiments, the weight ratio of the compatibilizer to the second filler component is about 1: 1 to about 20: 1, for example about 5: 1 to about 15: 1, or about 7.5: 1 to about 12.5: 1, for example about 10: 1. In one embodiment, the inorganic particulates of the functional filler are calcium carbonate, such as ground calcium carbonate, and the second filler component is uncoated carbon black. If a second filler component is used, it is about 0.1% to about 5% by weight of the polymer composition, eg, about 0.5% to about 4% by weight of the resin composition, or about 0.5% by weight ~ About 3 wt%, or about 0.5 wt% to about 2.5 wt%, or about 0.5 wt% to about 2 wt%, or about 0.5 wt% to about 1.5 wt%, or about 0.75 wt% to 1.25 wt% .
The second filler component may also serve to increase the density of the resin composition.
In certain embodiments, the second filler is at least about 0.5 wt%, such as about 0.5 wt% to about 10 wt%, or about 0.5 wt% to about 5.0 wt%, based on the total weight of the resin composition. %, Or from about 0.5% to about 2.5% by weight.

Impact Modifier In one embodiment, the resin composition comprises an impact modifier, such as up to about 20% by weight impact modifier, such as, for example, based on the total weight of the polymer resin. About 0.1 wt% to about 20 wt%, or about 0.5 wt% to about 15 wt%, or, for example, less than about 10 wt%, or about 1 wt% to about 10 wt%, based on the total weight of the resin composition %, Or about 2 wt% to about 5 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 7.5 wt%, or about 1.5 wt% to about 3.0 wt%, or about 2 wt% % To about 6% by weight, or about 2% to about 5% by weight of the impact modifier.
In one embodiment, the impact modifier is an elastomer, such as a polyolefin elastomer. In one embodiment, the polyolefin elastomer is a copolymer of ethylene and another olefin (eg, an α-olefin) such as octane and / or butene and / or styrene. In one embodiment, the impact modifier is a copolymer of ethylene and octene. In one embodiment, the impact modifier is a copolymer of ethylene and butene.
In one embodiment, the impact modifier is a recycled (eg, post-industrial) impact modifier.

In one embodiment, the above impact modifier, such as the above polyolefin copolymer such as ethylene octene copolymer, has a density of about 0.80 to about 0.95 g / cm ³ and / or about 0.2 g / 10 minutes (190 ° C. 2.16 kg) to about 30 g / 10 min (2.16 kg at 190 ° C.), for example about 0.5 g / 10 min (2.16 kg at 190 ° C) to about 20 g / 10 min (2.16 kg at 190 ° C), or about 0.5 g / 10 minutes (2.16 kg at 190 ° C.) to about 15 g / 10 minutes (2.16 kg at 190 ° C.), or about 0.5 g / 10 minutes (2.16 kg at 190 ° C.) to about 10 g / 10 minutes (2.16 kg at 190 ° C.) Or about 0.5 g / 10 min (2.16 kg at 190 ° C.) to about 7.5 g / 10 min (2.16 kg at 190 ° C.), or about 0.5 g / 10 min (2.16 kg at 190 ° C) to about 5 g / 10 Minutes (2.16 kg at 190 ° C.), or about 0.5 g / 10 min (2.16 kg at 190 ° C.) to about 4 g / 10 min (2.16 kg at 190 ° C.), or about 0.5 g / 10 min (2.16 kg at 190 ° C.) ) To about 3 g / 10 min (2.16 kg at 190 ° C.), or about 0.5 g / 10 min (2.16 kg at 190 ° C) to about 2.5 g / 10 min (2.16 kg at 190 ° C), or about 0.5 g / 10 Minutes (2.16 kg at 190 ° C.) to about 2 g / 10 min (2.16 kg at 190 ° C.), or about 0.5 g / 10 min (2.16 kg at 190 ° C.) Having an MFI of (2.16 kg at 190 ° C.) to about 1.5 g / 10 min. In such or certain embodiments, the impact modifier is an ethylene octene copolymer having a density of about 0.85 to about 0.86 g / cm ³ . An exemplary impact modifier is a polyolefin elastomer manufactured by DOW under the Engage (RTM) brand, such as Engage (RTM) 8842. In such embodiments, the formulated polymer blend can further include an antioxidant, as described herein. In such embodiments, the impact modifier is present in an amount of less than about 10% by weight, such as about 1% to about 7.5% by weight, or about 1.5% to about 3.0% by weight. Can.

In one embodiment, the impact modifier is a styrene and butadiene based copolymer, such as a linear block copolymer based on styrene and butadiene. In such embodiments, the impact modifier is about 1 to about 5 g / 10 min (5.0 kg at 200 ° C.), such as about 2 g / 10 min (5.0 kg at 200 ° C.) to about 4 g / 10 It can have an MFI of a minute (5.0 kg at 200 ° C.), or about 3 g / 10 min (5.0 kg at 200 ° C.) to about 4 g / 10 min (5.0 kg at 200 ° C.). In such embodiments, the linear block copolymer may be a recycled linear block copolymer.
In one embodiment, the impact modifier is a copolymer based on styrene and isoprene, such as a linear block copolymer based on styrene and isoprene. In such embodiments, the impact modifier is about 5 to about 20 g / 10 min (2.16 at 230 ° C.), such as about 8 g / 10 min (2.16 kg at 230 ° C.) to about 15 g / 10 min. It can have an MFI of (2.16 kg at 230 ° C.), or about 10 g / 10 min (2.16 kg at 230 ° C.) to about 15 g / 10 min (2.16 kg at 230 ° C.). In such embodiments, the linear block copolymer may be recycled.

In one embodiment, the impact modifier is a triblock copolymer based on styrene and ethylene / butene. In such embodiments, the impact modifier is about 15 g / 10 min (5.0 kg at 200 ° C.) to about 25 g / 10 min (5.0 kg at 200 ° C.), such as about 20 g / 10 min (200 ° C.). It can have an MFI of 5.0 kg) to about 25 g / 10 min (5.0 kg at 200 ° C.).
MFI can be measured according to ISO 1133.
In certain embodiments, for example, in embodiments where the impact modifier is a linear block copolymer based on styrene and butadiene, or styrene and isoprene, and / or the resin composition includes PE, It is crosslinked between the impact modifier and one or more polymers of the polymer resin. In some embodiments, the impact modifier may be miscible in the polymer blend.
In one embodiment, the impact modifier is an optionally recycled styrene butadiene styrene block copolymer (rSBS). In such embodiments, the rSBS may be present in the resin composition in an amount of about 2 wt% to about 5 wt%, based on the total weight of the resin composition.

Manufacturing Method The above resin composition can be manufactured by a method including blending the above polymer component, for example, polyethylene, polypropylene, with the above compatibilizer and other optional additives.
In one embodiment, the method comprises providing a recycled mixed polyolefin feed comprising polypropylene and polyethylene, combining the recycled mixed polyolefin feed with other sources of polyethylene and / or polypropylene. Also include, and blending.
The relative amounts of polyethylene, polypropylene and any other source of polyolefin can be selected to produce the resin composition described herein.
In one embodiment, the method comprises preparing, preparing or obtaining a compatibilizer, and combining with a mixture of different polymer types. The compatibilizer may be prepared by mixing the inorganic particulate material with the surface treatment / coupling agent in a suitable amount at a temperature of about 80 ° C. or less, as described herein. it can.
In one embodiment, the resin composition is a second filler component and / or impact modifier (eg, rSBS) and / or / and may be added prior to or during compounding of the resin composition and the compatibilizer. Or contains an antioxidant.

Formulation itself is a technique well known to those skilled in the art of polymer processing and manufacture. It is understood in the art that blending differs from blending or mixing processes performed at temperatures lower than those at which the components melt.
Compounding can be carried out using a twin screw compounder, for example, a Baker Perkins 25 mm twin screw compounder. The above polymer, compatibilizer and other optional additives may be premixed and supplied from a single hopper. Alternatively, at least the polymer and the compatibilizer may be fed from separate hoppers. The melt obtained can, for example, be cooled in a water bath and then pelletized. In one embodiment, the temperature during compounding is increased relative to the temperature at which the compatibilizer is prepared. In some embodiments, the temperature in the compound is about 150-250 ° C., such as about 160-240 ° C., or about 170-230 ° C., or about 170-220 ° C., or about 170-220 ° C., or about 200 ° C. It is in the range of -250 ° C. In certain embodiments, the temperature during compounding causes thermomechanical degradation of the polyolefin (eg, recycled polyolefin) to form macroradical fragments sufficient to react with the surface-treated inorganic particulate material Enough temperature to

  The formulated composition may further include additional components such as slip aids (eg, Erucamide), processing aids (eg, Polybatch® AMF-705), mold release agents and antioxidants. Suitable mold release agents are readily apparent to those skilled in the art and include fatty acids and zinc salts of fatty acids, calcium salts, magnesium salts and lithium salts and organophosphates. Specific examples are stearic acid, zinc stearate, calcium stearate, magnesium stearate, lithium stearate, calcium oleate and zinc palmitate. Slip aids and processing aids, and mold release agents may be added in amounts less than about 5% by weight based on the weight of the masterbatch.

Other Embodiments In one embodiment, the resin composition does not contain 24% by weight of polypropylene.
In one embodiment, the resin composition does not contain 56% by weight of HDPE.
In one embodiment, the resin composition does not contain 24% by weight of polypropylene and 56% by weight of polypropylene.
In one embodiment, the resin composition does not contain 20% by weight of surface-treated calcium carbonate, and the calcium carbonate may be ground calcium carbonate having ad ₅₀ of 0.8 μm and / or the calcium carbonate The surface throughput according to equation (1) applied to can be calculated to give a monolayer coating on the surface.
In one embodiment, the resin composition is not the polymer composition designated as Composition A. Composition A is a polymer composition comprising 20% by weight of surface-treated calcium carbonate, 56% by weight of HDPE, and 24% by weight of polypropylene,
(i) The surface-treated calcium carbonate is ground calcium carbonate (d ₅₀ = 0.8 μm) coated with a coupling regulator according to the formula (1), and the surface treatment amount applied to the calcium carbonate is calculated to calculate Give a single layer coating on the surface,
(ii) The above composition is prepared using a Baker Perkins 25 mm twin screw compounder, and
(iii) The HDPE and PP are from a recycled mixed polyolefin feed containing HDPE and PP derived from injection molding materials.
In one embodiment, the polymer resin is not in the form of polymer fibers.
In one embodiment, the article is not a polymer fiber.

Articles of Manufacture The above-described polymeric resins of the present invention as defined herein may be used to produce articles by injection molding of the above-described polymeric resins. In certain embodiments, the present invention relates to a method of making an article by injection molding comprising injection molding an article from the above-described polymer resin of the present invention as defined herein.
Any known injection molding method suitable for preparing an article in accordance with the present invention can be used. In one embodiment, injection molded articles can be prepared using Arburg Allrounder 320M, and then the molded articles can be conditioned at 23 ° C., 50% relative humidity for a minimum of 40 hours.
In one embodiment, the article is a portable waste or waste container, such as a wheelie bin, or part of a component thereof.
In one embodiment, the article of manufacture is a plastic pallet.
In certain embodiments, the article produced by injection molding of the polymer resin as defined herein comprises: (i) an article comprising the polymer resin without the compatibilizer and / or (ii) the article Compatibilizers have different and / or improved mechanical properties as compared to articles made from the above polymer resins replaced with polymer based compatibilizers.

In certain embodiments, the article made by injection molding of the polymer resin as defined herein has one or more of the following:
a) (i) an article comprising the polymer resin without the compatibilizer and / or (ii) compared to an article made from the polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer Do not include Tiger strike live or include Tiger strike live;
b) the flexural modulus, as measured according to ISO 178, is greater than the article made from the polymer resin, wherein the compatibilizer is replaced by a polymer based compatibilizer;
c) the flexural modulus has at least about 900 MPa, for example about 900 MPa to about 1200 MPa, as measured according to ISO 178;
d) Impact strength is greater than an article comprising the above polymer resin without the above compatibilizer, as measured by Izod notched impact test at 23 ° C. ± 2 ° C. according to ISO 180;
e) Impact strength is (i) greater than and / or a flexural modulus than an article comprising the above polymer resin without the above compatibilizer as measured by Izod notched impact test at 23 ° C. ± 2 ° C. according to ISO 180 (Ii) when measured according to ISO 178, the compatibilizer is greater than the article made from the polymer resin replaced with a polymer based compatibilizer;
f) Impact strength has at least about 4.0 kJ / m ² , for example about 4.0 kJ / m ² to about 20 kJ / m ² , as measured by Izod notched impact test at 23 ° C. ± 2 ° C. according to ISO 180.

In certain embodiments, the article produced by injection molding of the polymer resin as defined herein comprises (i) an article comprising the polymer resin without the compatibilizer and / or (ii) the phase Compared to articles made from the above polymer resin wherein the solubilizer is replaced by a polymer based compatibilizer, the tiger stripe is reduced or does not contain a tiger stripe.
Injection molded plastics often exhibit visible defects called tiger stripes, often with long flow lengths. Thus, the term "tiger stripe" means a defect present in the form of a band visible on the surface of an injection molded article. The stripes are typically alternating bands, such as bright bands, present on the surface of the injection molded article due to the unstable flow front, eg, poor bonding of the immiscible polymer resin. And dark bands or shiny bands and dull bands.
In certain embodiments, the compatibilizer as defined herein comprises (i) an article comprising the polymer resin without the compatibilizer and / or (ii) a polymer based phase in which the compatibilizer is based. By injection molding the above polymer resin as defined herein to eliminate or reduce tiger stripes as compared to articles made from the above polymer resin replaced with a solubilizer It can be used in the manufacture of articles.

In certain embodiments, the compatibilizer as defined herein eliminates (i) the occurrence of Tiger Stripe in an article made from the polymer resin by injection molding, or (ii) the compatibilization Reduce the occurrence of tiger stripes as compared to articles made from the above polymer resin that do not contain the agent and / or articles made from the above polymer resin in which the compatibilizer is replaced by the polymer based compatibilizer Can be used in the above-described polymer resins as defined herein.
In certain embodiments, the use of the polymer resin as defined herein in the manufacture of an article by injection molding of the polymer resin results in at least 50%, or at least 75%, or at least 50% of the visible presence of tiger stripes. It can be reduced by 90%, or at least 99%. In certain embodiments, the use of the polymer resin as defined herein in the manufacture of an article by injection molding of the polymer resin can eliminate the visible presence of tiger stripes in the manufactured article. .
In certain embodiments, the article made as defined herein comprises: (i) an article made from the above polymer resin that does not contain the compatibilizer and / or (ii) the compatibilizer It may have improved tiger stripe properties, eg, improved visible tiger stripe properties, as compared to articles made from the above polymer resins replaced with polymer based compatibilizers. In certain embodiments, the article made as defined herein comprises (i) an article made from the polymer resin that does not contain the compatibilizer or (ii) the compatibilizer is a polymer There may be less visible reduction of tiger stripes, eg, a reduction in the number of tiger stripes or visible tiger stripes, as compared to articles made from the above polymer resin replaced with a base compatibilizer.

The effect of the compatibilizer in the polymer resin due to the presence of the tiger stripe can be seen visually in FIGS.
In certain embodiments, the article produced by injection molding of the polymer resin as defined herein has a polymer wherein the compatibilizer is replaced by a polymer based compatibilizer as measured according to ISO 178. It has a flexural modulus greater than articles made from resin.
In certain embodiments, the article made by injection molding a polymer resin as defined herein has a flexural modulus of at least about 880 MPa, such as at least about 900 MPa, or at least about 925 MPa, or at least about 950 MPa. . In certain embodiments, the article produced by injection molding of the above-defined polymer resin as defined herein has a flexural modulus of about 900 to about 1200 MPa, such as about 925 to about 1175 MPa.
In certain embodiments, an article produced by injection molding of a polymer resin as defined herein is compared to an article produced from the above polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer. Thus, it has a flexural modulus of at least about 2% or more, such as at least about 5% or more, or at least about 10% or more. In certain embodiments, the article produced by injection molding of the polymer resin as defined herein is an article produced from the polymer resin wherein the compatibilizer is replaced with a polymer based compatibilizer. And a flexural modulus of at least about 50 MPa or more, such as at least about 75 MPa or more, or at least about 85 MPa or more.

In certain embodiments, the article produced by injection molding of a polymer resin as defined herein has a flexural modulus comparable to an article comprising the polymer resin without the compatibilizer, eg, The flexural modulus may be 10% or less than an article containing the polymer resin without the compatibilizer. In certain embodiments, the article produced by injection molding of the polymer resin as defined herein has a greater flexural modulus as compared to an article comprising the polymer resin that does not contain the compatibilizer. .
In certain embodiments, an article produced by injection molding of the above-defined polymer resin as defined herein, as measured according to (i) Izod notched impact test at 23 ° C. ± 2 ° C. according to ISO 180, Comparitive agent comparable to or greater than an article comprising a polymer resin without compatibilizer, and / or (ii) the compatibilizer is replaced by a polymer based compatibilizer as measured according to ISO 178 It has a greater flexural modulus than articles made from the above-described polymer resins.
In certain embodiments, the above-described article produced by injection molding of the above-described polymer resin as defined herein is the above compatibilized as measured by Izod notched impact test at 23 ° C. ± 2 ° C. according to ISO 180. It has a greater impact strength than an article comprising the above polymer resin which does not contain an agent.

In certain embodiments, the article produced by injection molding of the polymer resin as defined herein is at least 0.1 kJ / m as compared to an article comprising the polymer resin without the compatibilizer. ² large, such as at least 0.2kJ / m ² large, or at least 0.5kJ / m ² large, having at least 1 kJ / m ² greater, or at least 1.3 kJ / m ² greater impact strength.
In certain embodiments, the article produced by injection molding of the polymer resin as defined herein is at least 1% or more as compared to an article comprising the polymer resin that does not contain the compatibilizer. For example, it has an impact strength of at least 3% or more, or at least 5% or more, or at least 10% or more, or at least 25% or more.
In certain embodiments, the article produced by injection molding of the above-defined polymer resin as defined herein is at least about 4.0 kJ / m ² , such as at least about 4.2 kJ / m ² , such as at least about 5.0 kJ / m ² . m ^2, e.g., at least about 6.0kJ / m ^2, for example about 4.2kJ / m ² ~ about 20 kJ / m ^2, for example about 4.2kJ / m ² ~ about 10 kJ / m ^2,, about 4.2kJ / m ² ~ about 7.0 having kJ / m ² or about 5.0 kJ / m ² ~ about 7.0kJ / m ² or about impact strength of 6.0kJ / m ² ~ about 7.0kJ / m ^2,,.
In certain embodiments, the article produced by injection molding of the polymer resin as defined herein is an article produced from the polymer resin wherein the compatibilizer is replaced with a polymer based compatibilizer. Has comparable impact strength. In certain embodiments, the article made by injection molding of the polymer resin as defined herein is an article made from the polymer resin wherein the compatibilizer is replaced with a polymer based compatibilizer. And an impact strength of about 50% or less, such as about 40% or less, or about 30% or less.

In certain embodiments, an article produced by injection molding of the above-described polymer resin as defined herein has (i) an impact strength greater than an article comprising the above-described polymer resin that does not contain the above-mentioned compatibilizer. And / or (ii) has an impact strength comparable to an article made from the above polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer.
In one embodiment, the above-described article produced by injection molding of the above-described polymer resin as defined herein is (i) measured according to Izod notched impact test at 23 ° C. ± 2 ° C. according to ISO 180: Said compatibilizer is replaced by a polymer based compatibilizer having an impact strength greater than an article comprising said polymeric resin not comprising said compatibilizer and / or (ii) measured according to ISO 178 It has a greater flexural modulus than articles made from polymer resins.
In certain embodiments, the article produced by injection molding of the polymer resin as defined herein has an impact strength of at least about 4.0 kJ / m ² and a flexural modulus of at least about 900 MPa, eg, It has an impact strength of at least about 4.3 kJ / m ² and a flexural modulus of at least about 950 MPa.
In certain embodiments, the article produced by injection molding of the above-described polymer resin as defined herein has an impact strength of about 4 kJ / m ² to about 7 kJ / m ² and a flexural elasticity of about 900 MPa to about 1200 MPa. For example, it has an impact strength of about 4.3 kJ / m ² to about 6.5 kJ / m ² and a flexural modulus of about 950 MPa to about 1175 MPa.

In certain embodiments, the article produced by injection molding of the polymer resin as defined herein is (i) at least 0.1 kJ / m more than an article comprising the polymer resin without the compatibilizer. ² greater impact strength, eg at least 0.2 kJ / m ² , and / or (ii) at least 50 MPa greater, eg at least 50 MPa greater than an article made from the above polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer, eg It has a flexural modulus which is at least 80 MPa greater.
In certain embodiments, the article produced by injection molding of the polymer resin as defined herein is larger than the article comprising the polymer resin without the compatibilizer, eg, at least 0.1 kJ / m. ⁽ Ii) a flexural modulus comparable to, eg, less than or equal to, 10% greater than or equal to that of the above-mentioned polymer resin which does not contain the above ² large impact strength and / or at least 0.2 kJ / m ² high impact strength and Have.
In certain embodiments, the article produced by injection molding of the polymer resin as defined herein is an article produced from the polymer resin wherein the compatibilizer is replaced with a polymer based compatibilizer. Impact strength comparable to, eg less than or equal to 50%, or less than or equal to 30% and / or greater bending than articles made from the above polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer It has an elastic modulus.
In certain embodiments, an article made in accordance with the present invention comprises (i) an article comprising the polymer resin without the compatibilizer and / or (ii) the compatibilizer replaces the polymer based compatibilizer. It has an improved balance of impact strength and flexural modulus properties, such as an optimal balance of impact strength and flexural modulus properties, as compared to articles made from the above described polymer resins.

In one embodiment, the manufactured article is a portable waste or waste container, such as a willie bin, or a portion or component thereof, wherein the article comprises (i) the compatibilizer An article comprising the above-mentioned polymer resin not containing and / or (ii) the impact strength of the produced article as compared to an article produced from the above-mentioned polymer resin in which the above-mentioned compatibilizer is replaced by a compatibilizer based on polymer And the flexural modulus properties have an improved balance, the balance may be optimal.
The impact strength properties of the article correspond to the toughness of the article, ie the higher the impact strength of the article, the greater its toughness.
The flexural modulus properties of the article correspond to the stiffness of the article, ie the greater the flexural modulus of the article, the greater its stiffness.
Articles such as portable waste containers or waste containers, such as wheelie bins, require a balance of toughness and stiffness properties for optimal performance and properties.
In one embodiment, the compatibilizer as defined herein may be used in an article, and the article is injection molded of a polymer resin as defined herein comprising the compatibilizer. Manufactured by
(A) (i) an article manufactured by injection molding the above-mentioned polymer resin not containing the above-mentioned compatibilizer, or (ii) injection of a polymer resin in which the above-mentioned compatibilizer is replaced by the compatibilizer based on polymer Provide a balance of superior toughness and stiffness compared to articles produced by molding, or
(B) optimize the balance between toughness and stiffness of the article.

In one embodiment, the above-described compatibilizer as defined herein is used in a polymer resin as defined herein from which the article is manufactured by injection molding,
(A) (i) an article manufactured by injection molding the above-mentioned polymer resin not containing the above-mentioned compatibilizer, or (ii) injection of a polymer resin in which the above-mentioned compatibilizer is replaced by the compatibilizer based on polymer Provide a balance of superior toughness and stiffness compared to articles produced by molding, or
(B) optimize the balance between toughness and stiffness of the article.
In one embodiment, an article produced from the above polymer resin by injection molding has a tensile modulus and / or a tensile stress at yield, as measured according to ISO 527-2, which indicates that the compatibilizer is Larger than articles made from polymer resins replaced with polymer based compatibilizers.
In one embodiment, the polymer based compatibilizer is a copolymer. In one embodiment, the polymer based compatibilizer is a polypropylene based olefin block copolymer.
The above-described polymer resins of the invention as defined herein can be used to produce articles by techniques other than injection molding, such as extrusion of the above-mentioned polymer resins.

Example 1
As shown in Table 1 below, seven polymer resins were prepared, each containing a mixture of two HDPE and polypropylene (PP). All polymer resins were prepared by melt mixing with a Coperion ZSK ¹⁸ twin screw extruder (diameter 18 mm). The screw speed was set to 800 rpm and the feed speed was set to 8.0 kg / hour. The hot extrudate was immediately quenched in water and pelletized. Samples A and 1 are comparative examples because they were prepared without surface-treated inorganic particle material.

HDPE 1は3.3のMFI(g/10分、190℃で2.16kg)を有し；HDPE 2は4.6のMFI(g/10分、190℃で2.16kg)を有し；PPは6.4のMFI(g/10分、190℃で2.16kg)を有する。 table 1.

HDPE 1 has an MFI of 3.3 (g / 10 min, 2.16 kg at 190 ° C.); HDPE 2 has an MFI of 4.6 (g / 10 min, 2.16 kg at 190 ° C.); PP has an MFI of 6.4 (g / 10 min. g / 10 min, 2.16 kg at 190 ° C.).

Example 2
Melt flow index (MFI) properties of seven polymer resin samples were tested. MFI is the power rate (grams) produced in 10 minutes when a constant pressure is applied to the melt via the piston and a melt mass temperature of 190 ° C and 230 ° C with a total mass of 2.16 kg is applied . MFI was tested according to ISO 1133. The MFI properties of the above polymer resin samples 1 to 7 are shown in Table 2 below.

Table 2.

Example 3
Injection molded samples are prepared from the seven polymer resins prepared in Example 1 using Arburg Allrounder 320M, and the molded articles are tested at 23 ° C and relative humidity prior to procedure A (40/23/50) of Practice D 618 Conditioned at 50% for a minimum of 40 hours.
Each injection molded sample was then subjected to the following mechanical property test.
Bending test:
Bending tests were performed at room temperature using the Tinius Olsen Benchtop bending test according to ISO 178. The bending test results are shown in Table 3 below.
Tensile test:
Tensile tests were conducted at room temperature using a Tinius Olsen Benchtop tensile tester and the results shown correspond to an average of 8 measurements for each blend according to ISO 527-2. Table 3 below shows the tensile stress (MPa) and tensile modulus (MPa) at yield point of each injection molded sample.
Impact test:
Charpy notched impact testing can be performed at -20 ± 2 ° C. and 23 ± 2 ° C. using an Instron Ceast 9340 drop weight impact tester according to ISO 179. The Izod notched impact test was performed at 23 ° C. ± 2 according to ISO 180. The results shown in Table 3 below correspond to the average of the complete break measurements for each blend.

Table 3.

Claims (29)

  A method of producing an article by injection molding, the method comprising injection molding an article from a polymer resin, said polymer resin being of different types of recycled polymer, inorganic particle material and the surface of said inorganic particle material A process comprising: a compatibilizer comprising the above surface treatment agent; and wherein the polymer resin has an MFI at 3.16 kg / 190 ° C. of 3.0 g / 10 min or more.   In articles manufactured by injection molding a polymer resin comprising a compatibilizer, the tiger stripes are eliminated or compared to and / or compared to an article comprising said polymer resin lacking said compatibilizer Use of said compatibilizer for reducing tiger stripes as compared to an article produced by injection molding a polymer resin wherein the agent has been replaced by a polymer based compatibilizer The polymer resin comprises an inorganic particulate material and a surface treatment agent on the surface of the inorganic particulate material, the polymer resin comprises different types of recycled polymers, and the polymer resin comprising the compatibilizer comprises 3.0 g / 10, Said use with an MFI at 2.16 kg / 190 ° C. for more than a minute.   A compatibilizer in a polymer resin (i) eliminating the occurrence of tiger stripes in articles manufactured by injection molding from said polymer resin, or (ii) prepared from said polymer resin lacking said compatibilizer And / or its use to reduce the occurrence of tiger stripes as compared to articles produced by injection molding a polymer resin wherein said compatibilizer has been replaced by a polymer based compatibilizer Said compatibilizer comprises an inorganic particulate material and a surface treatment agent on the surface of said inorganic particulate material, said polymer resin comprises different types of recycled polymers and comprises said compatibilizer The use, wherein the polymer resin has an MFI at 2.16 kg / 190 ° C. of 3.0 g / 10 min or more. In an article produced by injection molding a polymer resin comprising a compatibilizer,
(A) (i) an article produced by injection molding the polymer resin lacking the compatibilizer, or (ii) injection of a polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer Provide a balance of superior toughness and stiffness compared to articles produced by molding, or
(B) optimize the balance between toughness and stiffness of the article,
Use of said compatibilizer for
The compatibilizer comprises an inorganic particulate material and a surface treatment agent on the surface of the inorganic particulate material, the polymer resin comprises different types of recycled polymers, and the polymer resin comprises the compatibilizer , Said use having an MFI at 2.16 kg / 190 ° C. of 3.0 g / 10 min or more. Use of a compatibilizer in a polymer resin that produces an article by injection molding,
(A) (i) an article produced by injection molding the polymer resin lacking the compatibilizer, or (ii) injection of a polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer Provide a balance of superior toughness and stiffness compared to articles produced by molding, or
(B) optimize the balance between toughness and stiffness of the article,
Said use for
The compatibilizer comprises an inorganic particulate material and a surface treatment agent on the surface of the inorganic particulate material, the polymer resin comprises different types of recycled polymers, and the polymer resin comprises the compatibilizer , Said use having an MFI at 2.16 kg / 190 ° C. of 3.0 g / 10 min or more.   6. A polymer resin according to any of the preceding claims, wherein the polymer resin comprises polyethylene and polypropylene, or a mixture of different types of polyethylene (e.g. HDPE, LDPE and / or LLDPE) and polypropylene, or a mixture of different types of HDPE and polypropylene. The method or use according to clause 1.   7. The method or use according to any one of the preceding claims, wherein the polymer resin comprises polypropylene in an amount of up to about 90% by weight, for example up to about 40% by weight.   8. The method or use according to any one of the preceding claims, wherein the polymer resin comprises polyethylene in an amount of at least about 10% by weight, for example at least about 60% by weight.   9. The method or use of any one of the preceding claims, wherein the polymer resin is free of virgin polymer.   The polymer resin further comprises an impact modifier, for example, in an amount of less than about 10% by weight, such as about 1% to about 7.5% by weight, or about 1.5% to about 3.0% by weight. The method or use according to any one of 9 to 9.   11. The method or use according to any one of the preceding claims, wherein the compatibilizer is present in an amount of about 5% to about 20% by weight, for example 8% to about 12% by weight. Wherein the inorganic particles is from about 2.5μm or less, for example, having about 1.0μm or less than about 0.75μm below the d _50, method or use of any one of claims 1 to 11. 13. The method or use according to any one of the preceding claims, wherein the surface treatment agent comprises or is a compound having the formula (1):
A- (XY-CO) _m (OB-CO) _n OH (1)
(In the formula,
A is a moiety containing a terminal ethylene bond having one or two adjacent carbonyl groups;
X is O and m is 1 to 4 or X is N and m is 1;
Y is C _1-18 -alkylene or C _2-18 -alkenylene;
B is C _2-6 -alkylene; n is 0 to 5;
However, when A contains two carbonyl groups adjacent to the ethylene group, X is N).   The method or use according to claim 13, wherein the compound is selected from β-carboxyethyl acrylate, β-carboxyhexyl maleimide, 10-carboxydecyl maleimide, 5-carboxypentyl maleimide and β-acryloyloxypropanoic acid.   The compatibilizer comprises an inorganic particle material and an organic linker on the surface of the particle, wherein the organic linker has an oxygen containing acid functionality and the organic linker is in the base form of an organic acid. 15. The method or use according to any one of 14.   16. The method or use according to any one of the preceding claims, wherein the inorganic particles are calcium carbonate, for example ground calcium carbonate.   17. The method or use of any one of claims 1-16, wherein the polymer resin further comprises an antioxidant in an amount less than about 5% by weight, such as less than about 1% by weight.   18. The method or use according to any one of the preceding claims, wherein the article is a portable waste or waste container, for example a wheelie bin, or a part or component thereof.   A polymer resin suitable for use in the manufacture of articles by injection molding, wherein said polymer resin is about 5% by weight to about 20 based on the mixture of different recycled polymers and the total weight of said polymer resin. Said polymer resin comprises, by weight, an inorganic particle material and a compatibilizer comprising a surface treatment agent on the surface of said inorganic particle material, said polymer resin having an MFI at 3.06 / 10 2 or more at 2.16 kg / 190 ° C. Said polymer resin is at least about 50% by weight recycled polyethylene, based on the total weight of the polymer composition, and about 10% by weight to about 30% by weight based on the total weight of said polymer resin Said polymer resin, comprising polypropylene.   20. The polymeric resin of claim 19, further comprising an impact modifier, for example, in an amount of less than about 10 wt%, such as about 1.0 wt% to about 7.5 wt%, based on the total weight of the polymeric resin.   21. The polymer resin of claim 19 or 20, further comprising an antioxidant, for example, in an amount of less than about 5 wt%, such as about 0.1 wt% to about 1.0 wt%, based on the total weight of the polymer resin. Wherein the inorganic particulate material, approximately 2.5μm or less, for example about 1.0μm or less, or about 0.75μm having the following d _50, claim 19 to 21, set forth in any one polymer resin. The polymer resin according to any one of claims 19 to 22, wherein the surface treatment agent comprises or is a compound having the formula (1):
A- (XY-CO) _m (OB-CO) _n OH (1)
(In the formula,
A is a moiety containing a terminal ethylene bond having one or two adjacent carbonyl groups;
X is O and m is 1 to 4 or X is N and m is 1;
Y is C _1-18 -alkylene or C _2-18 -alkenylene;
B is C _2-6 -alkylene; n is 0 to 5;
However, when A contains two carbonyl groups adjacent to the ethylene group, X is N).   24. The polymer resin of claim 23, wherein said compound is selected from beta-carboxyethyl acrylate, beta-carboxyhexyl maleimide, 10-carboxydecyl maleimide, 5-carboxypentyl maleimide and beta-acryloyloxypropanoic acid.   20. The compatibilizer comprises an inorganic particle material and an organic linker on the surface of the particle, wherein the organic linker has oxygen containing acid functionality and the organic linker is in the base form of an organic acid. 24. A polymer resin according to any one of 24.   26. The polymer resin of any of claims 19-25, wherein the inorganic particles are calcium carbonate, such as ground calcium carbonate.   An article manufactured by injection molding the polymer resin according to any one of claims 19 to 26 or obtainable by the method according to any one of claims 1 to 18. 28. The article of claim 27, having one or more of the following:
a) (i) an article comprising the polymer resin lacking the compatibilizer, and / or (ii) an article made from the polymer resin composition wherein the compatibilizer is replaced by a polymer based compatibilizer Does not contain reduced Tiger Stripes, or Tiger Stripes, as compared to;
b) a flexural modulus greater than an article made from the polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer, as measured according to ISO 178;
c) a flexural modulus of at least about 900 MPa, for example about 900 MPa to about 1200 MPa, as measured according to ISO 178;
d) Impact strength greater than an article comprising said polymeric resin lacking said compatibilizer, as measured according to ISO 180 according to an Izod notched impact test at 23 ° C. ± 2 ° C .;
e) (i) greater impact strength than an article comprising said polymer resin lacking said compatibilizer, and / or (ii) measured according to ISO 180 according to the Izod notched impact test at 23 ° C. ± 2 ° C. Greater flexural modulus than articles made from the polymer resin wherein the compatibilizer is replaced by a polymer based compatibilizer, as measured according to ISO 178;
f) Impact strength of at least about 4.0 kJ / m ² , for example about 4.0 kJ / m ² to about 20 kJ / m ² , as measured by Izod notched impact test at 23 ° C. ± 2 ° C. according to ISO 180.   29. An article according to claim 27 or 28, wherein the article is a portable waste or waste container, for example a wheelie bin, or a part or component thereof.

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